期刊
CHEMCATCHEM
卷 5, 期 8, 页码 2330-2335出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201200944
关键词
alkynes; arenes; carbene ligands; gold; steric hindrance
资金
- Universitat Heidelberg
- Landesgraduiertenakademie
- DFG [SFB 623]
- Fonds der chemischen Industrie FCI
An N-heterocyclic carbene gold complex IPr**AuN (2) has been synthesized, spectroscopically investigated, structurally characterized, and used as a highly active and stable catalyst in the Hashmi phenol synthesis (IPr**=1,3-di-p-tolylimidazol-2-ylidene with four di-tert-butylbenzhydryl ortho substituents, Tf = trifluoromethansulfonyl). A side reaction comprises an irreversible arene oxide ring opening with subsequent 1,2 methyl shift. The advantage of the steric demand of the ancillary ligand was explained by higher equilibrium concentrations of the cationic gold species, the circumvention of inactive dinuclear intermediates, and the inhibition of catalyst decomposition pathways. The methanol addition-hydration of alkynes featured a turnover-limiting proton transfer step of an alkenylgold catalyst resting state, indicated by a large primary kinetic isotope effect and an alkyne competition experiment.
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